title: Charged states of 1,3,5-triazine molecules as models for star-shaped molecular architecture: a DFT and spectroelectrochemical study.
abstract: The density functional theory calculations of molecular structure and spectroscopic and electronic properties of charged states in four triazine-heteroaryl star-shaped compounds are presented. The molecules end-capped with different heteroaryl groups, i.e., thiophene (TTT1), furan (TFT2), 3,4-ethylenedioxythienyl (TET3), and thiazole (TSNT4), were studied by electrochemical and in situ ESR/UV-vis-NIR spectroelectrochemical techniques in tetrahydrofuran/(TBA)BF(4). The charged states of monomers were created by cathodic reduction and the stability of generated anion radicals was characterized in detail both experimentally and theoretically. The TET3 molecule resulted in a star-shaped hyperbranched polymer formed anodically which in turn can be reversibly oxidized up to the tetracation. The nature and charge distribution of charge carriers at each redox state in the as-prepared polymer was clarified by calculations for the model (TET3)(3) trimer structure.
authors.affiliation: Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinskeho 9, SK-81237 Bratislava, Slovak Republic. vladimir.lukes@stuba.sk
authors.forename: Vladimir
authors.initials: V
authors.lastname: Lukeš
authors.forename: Peter
authors.initials: P
authors.lastname: Rapta
authors.forename: Krzysztof R
authors.initials: KR
authors.lastname: Idzik
authors.forename: Rainer
authors.initials: R
authors.lastname: Beckert
authors.forename: Lothar
authors.initials: L
authors.lastname: Dunsch
mesh_terms: D004578:Electron Spin Resonance Spectroscopy; D005663:Furans / Q000737:chemistry; D008958:Models, Molecular; D011789:Quantum Theory; D013056:Spectrophotometry, Ultraviolet; D013876:Thiophenes / Q000737:chemistry; D014227:Triazines / Q000737:chemistry*
chemical_list: D005663:Furans; D013876:Thiophenes; D014227:Triazines; C039281:furan